Metal-containing azo dyestuffs



United States 3,007,913 METAL-CONTAINING Alt) DYETUFFS Piero Maderni andHans Ruckstuhl, Basel, Switzerland,

assignors, by mesne assignments, to Saul & C0., Newark, N.J., as nomineeof Fidelity Union Trust Company, executive trustee under Sandoz Trust NDrawing. Filed Jan. 25, 1954, Ser. No. 406,084-

Claims priority, application Switzerland Jan. 29, 1953 8 Claims. (Cl.260-146) stands for the residue of a coupling component free of sulfonicand carboxylic acid groups and chosen from 3- methyl-S-pyrazolones,acetoacetylamino-alkanes, acetoacetylami no-aryl derivatives of thebenzene and naphthalene series, and hydroxy-aryl derivatives of thehenzene and naphthalene series, whereby is in ortho-position to -N=N,and x stands for hydrogen, halogen, nitro or lower alkyl.

vThese new dyestuffs are obtained by coupling one mol atent O BJW'LQIBPatented Nov. 7, 1961 of the diazo compound of a Z-aminobenzene sulfonicacid morpholylamide of the formula wherein x stands for hydrogen,halogen, nitro or lower alkyl, and y stands for hydroxy or lower alkoxy,

with one mol of a coupling component free of sulfonic and carboxylicacid groups and chosen from 3-methyl- S-pyrazolones,acetoacetylamino-alkanes, acetoacetylamino-aryl derivatives of thebenzene and naphthalene series, and hydroXy-aryl derivatives of thebenzene and naphthalene series, whereby the enolic or phenolic hydroxygroup stands in ortho-position to the carbon atom capable of coupling,and by treating the thus-obtained monoazo compound with achromium-yielding agent.

The coupling of the diazo compounds with the azo components as well asthe working up and the separation of the resulting products areadvantageously carried out in a neutral or weakly alkaline medium. Whenusing the l-hydroxy-naphthalenes as azo components, it is preferable towork in a caustic alkaline medium; thus, coupling takes place inortho-position to the hydroxy group. The conversion of the monoazocompounds into the chromium-containing azo dyestuffs is effected withe.g. the salts of chromium such as chromium fluoride, chromium sulfate,chromium formate, chromium acetate, potassium chromium sulfate andammonium chromium sulfate, either in an aqueous suspension or solutionor in an organic medium, e.g. in formamide or in a melt of an alkalimetal salt of an aliphatic monocarboxylic acid having a low molecularweight. Metallization in an aqueous caustic alkaline medium isespecially advantageous, in which case the metal salts are added in thepresence of such compounds, as maintain the chromium in solution in thecaustic alkaline medium in complex combination, as, e.g., tartaric acid,citric acid, or lactic acid. For the preparation of the chromium complexcompounds there are also suitable the chromates, as e.g. sodiumchromate, potassium chromate, sodium bichromate and potassiumbichromate. The chroming of the monoazo dyestuffs with chromates iseifected in a strong alkaline medium. If the monoazo compound containsan alkoxy group as a group favourable to metal complex formation, thenthe metallization is advantageously carried out in an organic solvent,for example in a glycol such as ethylene glycol, ethylpolyglycol, orbutylpolyglycol, and in the presence of an acid-binding agent such assodium acetate.

It has also been found that particularly valuable metalcontaining azodyestuffs are obtained if less than one atom of metal is used for eachmolecule of the monoazo compound, especially if the so-called 1:2complexes are produced, wherein about one atom of metal is present fortwo molecules of azo compounds.

The resulting metal-containing azo dyestuffs are separated out from theaqueous medium by the addition of salt, if desired after pouring theorganic metallizing solution into water, being thereupon filtered off,washed and dried. Many of these dyestufis possess an outstanding powerof exhaustion from neutral dyebaths; therefore they generally dye Woolfrom neutral and silk from weakly acid dyebaths in level and richyellow, brown-yellow, orange, red, bordeaux, violet and gray shades ofvery good fastness to milling and washing and of most excellent fastnessto light. The new dyestuffs are also valuable for the dyeing of leatherand particularly of nitrogenous artificial fibers such as the syntheticpolyamide fibers, e.g. nylon, Perlon.

The following examples illustrate the invention without limiting it.Therein the parts denote parts by Weight, the percentages percentages byweight, and the temperatures are given in degrees centigrade.

EXAMPLE 1 25.8 parts of 1-hydroxy-2-aminobenzene-4-sulfonic acidmorpholylamide are diazotized indirectly in the usual manner andcombined with 20.9 parts of 1-(3-chloro)- phenyl-3-metl1yl- 5-pyrazolone in an aqueous solution made alkaline with sodium carbonate.The resulting monoazo compound precipitates immediately. It is filtered,washed and dried and is a brown-red powder which dissolves inconcentrated sulfuric acid with a yellow color and in dilute sodiumcarbonate solution with a yellow-orange color.

In order to form the chromium-containing azo dyestuff, 47.8 parts of thedried monoazo compound are dissolved in 600 parts \of water with 80parts of sodium hydroxide solution at 95. A mixture of parts of sodiumbichromate and 75 parts of water, made neutral with sodium hydroxide, isadded to the solution. The material is boiled under reflux until thedyestuff is completely metallized. The dyestuif is isolated from thealkaline solution by salting out and filtration. The driedmetal-containing azo dyestufi is a brown-red powder which dissolves inconcentrated sulfuric acid giving a yellow color and in Water giving ared-orange color. It corresponds to the formula and dyes wool, silk andpolyamide fibers from a neutral to acetic acid bath in rich orangeshades. The dyeings have an excellent fastness to milling, washing andlight.

EXAMPLE 2 25.8 parts of 1-hydroxy-2-aminobenZene-4-sulfonic acidmorpholylarnide are diazotized indirectly in the usual manner andcombined with 26.7 parts of 1-phenyl-3- methyl-5-pyrazolone-3'-sulfonicacid methylamide in an aqueous solution made alkaline with sodiumcarbonate. The resulting red monoazo compound is filtered and dried. Itdissolves in concentrated sulfuric acid with a yelloworange color. Thechromium-containing azo dyestufi prepared according to the data ofExample 1 is a brown-red powder which dissolves in concentrated sulfuricacid with a yellow color and in water with an orange color. Itcorresponds to the formula and dyes wool, silk and synthetic polyamidefibers from neutral to acetic acid baths in rich orange shades ofexcellent fastness to milling, washing and light.

EXAMPLE 3 27.2 parts of l-methoxy-Z-aminobenzene 4 sulfonic acidmorpholylamide are diazotized indirectly. The diazo suspension is runinto a solution of 24 parts of l-carbethoxyamino-7-hydroxynaphthalene,14 parts of a 30% sodium hydroxide solution, 20 parts of sodiumcarbonate and 670 parts of water at 0-2". Within 2 hours the re actionmixture is added to 22.5 parts of a 30% sodium hydroxide solution andthen stirred until the coupling is completed. The resulting monoazocompound is precipitated by the addition of sodium chloride to thereaction mixture, subsequently filtered and dried.

The monoazo compound is converted into the chromium complex by heatingit for 3 hours with 25 parts of potassium chromium (III) sulfate and 600parts of formamide to 130; the chromium-containing azo dyestufi' is thenisolated in the usual manner. It corresponds to the formula anddissolves in concentrated sulfuric acid with a bluishred, in hot waterwith a gray-blue color, and dyes Wool, silk and synthetic polyamidefibers from a neutral to weakly acid bath in gray shades fast tomilling, washing and light.

In order to carry out the de-alkylating chroming process there may beused instead of formamide as an organic solvent also glycols such asethylene glycol, ethylpolyglycol or butylpolyglycol.

In the following table further examples are enumerated. The dyestufiiscan be obtained by coupling the diazotized1-hydroxy-2-aminobenzene-sulfonic acid morpholylarnide (column II of thetable, Diazo component) with an azo component which is free of sulfonicacid and carboxylic acid groups and possesses an enolic or phenolichydroxy group in ortho-position to the carbon atom capable of coupling(column III of the table, Azo componen stuffs are characterized in thecolumn IV of the table the shades of dyeings produced by the chromiumcomplex) Table wherein stands for the residue of a coupling componentfree of Example Nr. (I)

Monoazo compound Diazo component (11) A component (III) Shade of dyeingson Woolchromium complex (IV) 4 1-hydroxy-2-an1inobenzene-4-su1fonic acidl-(2.5-dichloro)phenyl-3-methyl-5-pyrazoorange.

morpholylamide. lone.

d 3-methy1-5-pyrazolone Do. 1-phenyl-3-methyl-fi-pyrazolone Do.1-(4-methyl)-pheny1-3-methyl-s-pyrazolone- Do.

3sullonic acid methylamide. 1-(3-ethyl)-phenyl-3-methyl-5-pyraz0lone Do.1-(4-chloro)-pheny1-3-methyl-5-pyrazolone- Do.

3-sulfonic acid ethylamide. l (5 .6 .7 .8 tetrahydro) naphthylfl) 3 D0.

rnethyl-5-pyrazo1one. 1 deeahydronaphthyl(2) 3 methyl 5 py Do. razolonc.l-acctoaeetylamino-3-chlorohenzene yellow. 1 acetoacetylamino -3 oyano-4- methylben 0.

zone.

14 do l-acetoacetylaminonaphthalene Do.

15 1-hydroxy-2-arninobenzene-4-su1fonic acidZacetoacetylaminonaphthalene Do.

morpholylamide.

16 do l-acetoacetylaminooctane Do.

1-hydroxy-2-acety1aminotmethylbenzene. brown.1-hydroxy-2-pr0pionylaminohenzene-4-tert. Do.

butylbenzene. l-hydroxy-ZA-dimethylbenzene Do.Z-hydroxynaphthalene-G-sulfonic acid amide. brown-violet.l-acetylamino-7-hydroxynaphthalene gray. l-carb0(2-ethoxy)-ethoxyamino-7-hydroxy- Do.

naphthalene.

23 do l-hydroxy-fi.S-dichloronaphthalcne dull violet.

241-hydroxy-2-amino-6-bromobenzene-4-snll-phenyl-3methyl-5-pyrazolone-3snlfonicorange.

fonic acid morpholylamide. acid methylamide.

25 do 1phenyl-3-methyl-5-pyrazolone-3-sulfonic Do.

acid-(3-methoxy)-propylamide.

26 1-hydroxy-2-amino-6-ohlorobenzene-4-sul-1-phenyl-3-n1ethyl-5-pmazolone-4-sulfonio Do.

fonic acid morpholylamide. acid-(3-sulfamido)-phenylamide.

27 do aeetoacotylaminobenzene yellow.

28 1-hydroxy-2-amino-6-nitrobenzcne-4-su1- 1-phenyl-3-methyl5-pyrazolone-4-sulfonic orange.

fonic acid morpholylamide. acid- (3 -sulfamido)-phenylamide.

29 do l-acetylamino-7-hydroxynaphthalene gray.

30 1-hydroxy-2-amino-6-methylbenzene-4-sulaeetoacetylaminohenzeneyellow.

fonic acid morpholylamide.

EXAMPLE 31 sulfomc and carboxyhc acid groups and selected from A dyebathis made up from the following: 500 parts of water, 1 part of anhydroussodium sulfate and 02 part of the dyestufi obtained in Example 2. 10parts of prewetted wool are placed into this dyebath at 30 and thedyebath is brought to 100 during approximately 15 minutes. Thistemperature is maintained for 60- minutes and during this time a further0.2 part of concentrated acetic acid is added. The dyeing is thenremoved from the bath, rinsed and dried.

The dyestufis prepared in the remaining examples are used to producedyeings in a similar manner.

Having thus disclosed the invention what is claimed the group consistingof 3-methy1-5-pyraz-olones, acetoacetylamino-alkanes,acetoacetylaminoeryl derivatives of the benzene and naphthalene series,and hydroXy-aryl derivatives of the benzene and naphthalene series,

being in ortho-position to N=N, and x stand for a member selected fromthe group consisting of hydrogen, halogen, nitro and lower alkyl.

2. The metal-containing azo dyestufi which corresponds to the formula 1.A chromium-containing azo dyestufi which corresponds to the formula/H2OH2C /H2CH2C /N-O2IS 0\ N02S (3113 01 11204120 H 11204120 C==N N=1 IR N=I -O=C I a L a I 0 t 5 0 O F a o on T on I I l l R 1 =N- c=o-1 I=NCHz-CH: (13] N=(]) I CH2-CH2 SO2N O HaC SO2N O CH2CH7 CH2CH3 I 7 8 l 3.The metal-containing azo dyestuff which corresponds 6. An azo dyecontaining one atom of chromium in L to the formula complex union withtwo mols of a compound correspond- I 13204120 7 ing to the formula N-msom 0H l soz-Nfiom H,C-H,o C=N\ N=N R I N=1:TC=C

E (l) S02 \i I 1110 CH: C=O-N=N 1 O wherein R is an aromatic radical ofthe naphthalene N=O CHE-G H2 series containing an OH group ortho to theazo bridge. H3CHN OS 5; SOPN 0 7. An azo dye containing one atom ofchromium in GB g complex union with two mols of a compound correspondingto the formula 4. The metal-containing azo dyestufi WhlCh corresponds OHHO to the formula Hz C -H:C N=N o N 0,s o o 0 can! H Ego-H O l T so,000m N=Nfl ll;

l B B2(|3/ on: H20 CH;

a 8. An azo dye contaimng one atom of chromium in ILI=N complex unionwith two mols of a compound corresponding to the formula CHrCH:

( 11 HO E5090 0 (L S 0:|N/ \O N=N OHQ-Ofi,

5. An azo dye containing one atom of chromium in Or I it complexunionwith two mols of a compound corresponding to the formula H2O CH1N=NR 113( 312 References Cited in the file of this patent UNITED STATESPATENTS 2,224,144 Dickey et al Dec. 10, 1940 2 on 2,251,813 West et a1Aug. 5, 1941 g 5 2,638,707 Brassel July 13, 1954 2,734,895 Zickendrahtet al Feb. 14, 1956 wherein R is an aromatic radical of the benzeneseries FOREIGN PATENTS containing an OH group ortho to the azo bridge.513,489 Belgium Feb. 13, 1953

1. A CHROMIUM-CONTAINING AZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 